Synlett 2014; 25(19): 2761-2764
DOI: 10.1055/s-0034-1379232
letter
© Georg Thieme Verlag Stuttgart · New York

Iridium–SYNPHOS-Catalyzed Hydrogenation through Dynamic Kinetic Resolution of α-Amino β-Keto Ester Hydrochlorides

Pierre-Georges Echeverria
a   PSL Research University, Chimie ParisTech-CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France   Fax: +33(1)44071062   Email: phannarath.phansavath@chimie-paristech.fr   Email: virginie.vidal@chimie-paristech.fr
,
Charlène Férard
a   PSL Research University, Chimie ParisTech-CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France   Fax: +33(1)44071062   Email: phannarath.phansavath@chimie-paristech.fr   Email: virginie.vidal@chimie-paristech.fr
,
Johan Cornil
b   Laboratoire de Chimie Organique, Institute of Chemistry, Biology and Innovation (CBI) – UMR 8231 ESPCI ParisTech/CNRS/PSL* Research University, 10 rue Vauquelin, 75231 Paris Cedex 05, France   Fax: +33(1)40794662   Email: janine.cossy@espci.fr
,
Amandine Guérinot
b   Laboratoire de Chimie Organique, Institute of Chemistry, Biology and Innovation (CBI) – UMR 8231 ESPCI ParisTech/CNRS/PSL* Research University, 10 rue Vauquelin, 75231 Paris Cedex 05, France   Fax: +33(1)40794662   Email: janine.cossy@espci.fr
,
Janine Cossy
b   Laboratoire de Chimie Organique, Institute of Chemistry, Biology and Innovation (CBI) – UMR 8231 ESPCI ParisTech/CNRS/PSL* Research University, 10 rue Vauquelin, 75231 Paris Cedex 05, France   Fax: +33(1)40794662   Email: janine.cossy@espci.fr
,
Phannarath Phansavath*
a   PSL Research University, Chimie ParisTech-CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France   Fax: +33(1)44071062   Email: phannarath.phansavath@chimie-paristech.fr   Email: virginie.vidal@chimie-paristech.fr
,
Virginie Ratovelomanana-Vidal*
a   PSL Research University, Chimie ParisTech-CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France   Fax: +33(1)44071062   Email: phannarath.phansavath@chimie-paristech.fr   Email: virginie.vidal@chimie-paristech.fr
› Author Affiliations
Further Information

Publication History

Received: 21 July 2014

Accepted after revision: 11 September 2014

Publication Date:
16 October 2014 (online)


Abstract

The stereoselective synthesis of anti β-hydroxy α-amino esters by iridium–SYNPHOS-catalyzed asymmetric hydrogenation of α-amino β-keto ester hydrochlorides is reported. The reaction proceeded through dynamic kinetic resolution to afford a variety of β-hydroxy α-amino ester derivatives with good yields and high ­level of diastereo- and enantioselectivities (de up to 99%, ee up to 92%).

 
  • References and Notes


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      Substrates 2ak were prepared according to procedures reported in ref. 6b and in the references thereafter:
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  • 14 Typical Procedure for the Ir-SYNPHOS-Catalyzed Asymmetric Hydrogenation of α-Amino-β-Ketoester Hydrochlorides: To a Teflon tube charged with α-sub-stituted β-keto ester 2 (0.44 mmol), NaOAc (36 mg, 0.44 mmol, 1 equiv) and AcOH (2 mL), was added solid catalyst [{Ir(H)[(S)-SYNPHOS]}2(μ-I)3]I (15 mg, 7 μmol, 1.5 mol%) in one portion and the reaction mixture was subjected to three vacuum/argon cycles. Under a flow of argon, the reaction vessel was placed in a stainless steel parallel hydrogenation system equipped with a central mechanical stirrer. The atmosphere of the autoclave was purged three times with argon and twice with H2. The temperature was adjusted to 40 °C and the autoclave was filled with H2 (100 bar). After 24 h of reaction, the autoclave was adjusted to r.t. and atmospheric pressure and finally purged three times with argon. The resulting mixture was concentrated under reduced pressure. The conversion was determined by 1H NMR analysis of the crude product. To a solution of the previous β-hydroxyester hydrochloride (0.44 mmol, 1 equiv) in anhyd CH2Cl2 (2 mL) were added benzoyl chloride (67 mg, 55 μL, 1.1 equiv) and Et3N (134 mg, 190 μL, 3 equiv) at 0 °C. The reaction mixture was stirred at 0 °C for 1.5 h and for 1 h at r.t., then diluted with CH2Cl2, quenched with sat. aq NH4Cl, extracted with CH2Cl2 and dried over MgSO4. The crude protected product was purified by flash chromatography to afford compound 3. The diastereomeric ratio was determined by 1H NMR analysis of the crude product, and the enantiomeric ratio was determined by chiral SFC analysis of the purified product using a Chiralcel OD-H, Chiralpak IA, IC or AD-H column.